Epithio dienamides

ABSTRACT

NOVEL EPITHIO SUBSTITUTED HYDROCARBON ESTERS, DERIVATIVES THEREOF, AND AMIDES HAVING DIUNSATURATION, SYNTHESIS THEREOF, USEFUL FOR THE CONTROL OF INSECTS

nited States Patent ice Patented Nov. 27, 1973 In the description hereinafter, each of R through R, 3,775,432 m and n is as defined hereinabove. EPITHIO DIENAMIDES The compounds of Formula A can be prepared ac- John B. Siddall and Clive A. Henrick, Palo Alto, Calif.,

cordin to the followin o tlined o assignors to Zoecon Corporation, Palo Alto, Calif. g g u pr cess Nti llirawing. Original applicatiolr LdHZILNSIer. 5 R: r

674 now Patent No. ate ar. 1973. Divided and this a liation Aii 18, 1972, S61: Hi).bH- cH.)..-on=on-d=on-R No. 281,669 0 (B) Int. Cl. C076 59/00 U.S. (:1. 260-327 E 7 Claims 10 l ABSTRACT OF THE DISCLOSURE Novel epithio substituted hydrocarbon esters, deriva- -d fl tives thereof, and amides having diunsaturation, synthesis s (A) thereof, useful for the control of insects.

In the practice of the above process, an epoxide of Formula B is reacted with potassium thiocyanate or ammonium thiocyanate in an organic solvent, such as lower alcohol, e.g. ethanol, to yield an episulfide of Formula A. The reaction is usually done above room temperature to This is a division of application Ser. No. 111,674, filed Feb. 1, 1971 now US. Pat. No. 3,723,462 issued Mar. 27, 1973. 2

This invention relates to novel unsaturated aliphatic r fl temperature f the reaction mixturehydrocarbon esters, amides and derivatives thereof useful The compounds f Formula B are prepared as d for the Colltf 01 0f Insects 0f the fOHOWlIlg Formula A! scribed in our copending applications Ser. Nos. 111,766

R5 R2 R now abandoned and 111,769, filed on even date, entitled A} (B A} Novel Compositions and Novel Products, respec- R- H(C :)s- H( i)mtively, the disclosures of which are hereby incorporated I (A) by reference.

The term cycloalkyl, as used herein, refers to a cyclic wherem: alkyl group of four to eight carbon atoms. The term R is hydrogen or alkyl; aralky refers to a monovalent group in which an aryl Each of R R and R is alkyl; group is substituted for a hydrogen atom of an alkyl m is zero or the positive integer one, two or three; group, Such as YL Y Y mesityl, P y y methn is the positive integer one, two or three; and Ylbenzyl, naphthylmethyl and p y y 5 is one f the groups; The term alkyl, as used herein, refers to a straight R1 or branched chain saturated aliphatic hydrocarbon group E F: having a chain lenth of one to twelve carbon atoms, such -oR or N as methyl, ethyl, n-propyl, i-propyl, n-butyl, n-hexyl,

n-amyl, n-heptyl, n-octyl, n-nonyl, lauryl, n-decyl, t-amyl,

or 3-ethylpentyl and Z-methylhexyl. The term hydroxyalky as used herein, refers to an alkyl group substituted with one hydroxy group, e.g. hydroxymethyl, p-hydroxyethyl and 4-hydroxypentyl. The term alkoxyalkyl, as

in which R is hydrogen, alkyl, cycloalkyl, aralkyl or metal cation; and each of R" and R is hydrogen, alkyl, cycloalkyl, aralkyl, phenyl, alkenyl, hydroxyalkyl,

used herein, refers to an alkyl substituted with one alkoxy alkoxyalkylor, when taken together w1th the mtrogen group e g methoxymethyl, z methoxyethyl, 4 ethoxy atom to WhlCh they are attached, pyrrolidmo, morphoe lino Piperidino piperazino or 4 alkylpiperazin butyl, n-propoxyethyl and t-butylethyl. The term alkenyl, as used herein, refers to an ethylenically un- The compounds of Formula A are us u for the Control saturated hydrocarbon group, branched or straight chain, of insects The compounds are pp using either liquid having a chain length of two to tweleve carbon atoms, e.g. or solid carriers, such as water, acetone, cottonseed oil, an vinyl, 3-butenyl, Z-butenyl, Z-hexenyl and i-propenyl. xylene, mineral oil, silicon, talc, natural and synthetic Whenever any of the foregoing terms are modified by resins, and the like. Generally, compositions for applicath d l r, th h i length f the group i t t i contain p to about of the active compound more than six carbon atoms with the exception of lower and more usually less than 25%, sufiicient composition alkoxyalkyl in which event a total chain length of twelve should be applied to provide from about 0.1 to 25 microcarbon atoms is the maximum. grams of the ac ive comp n P insect ypical insects The following examples are provided to illustrate the controlled by the present invention are Diptera, such as practice of the present invention. Temperature is given in mosquitos and houseflies; Hemiptera, such as Pyrrhodegrees centigrade. coridae and Miridae; and Coleoptera, such as Tenebrioni- EXAMPLE 1 dae, Crysomelid-ae and Dermestidae. For example, Pyrrhocoris apterus, Lygus hesperus, Tenebrio molitor, To 0.60 g. of ethyl 10,l1-0X i y Triboleum confusm, Diabrotica duodecimpunctata, Der- 2,4-dienoate in 25 ml. of absolute ethanol is added 5 mestes maculatus, Aedes aegypti and Musca domestica. ml. of water and 1.0 g. of potassium thiocyanate. The Without any intention of being bound by theory, the mixture is heated at reflux for about hours. Refluxing compounds of Formula A are believed to be eflective by 65 is stopped and the mixture poured into brine and extracted reason of hormonal action in that unlike conventional with ether. The ethereal extract is washed with brine,

insecticides which are effective by reason of causing imdried and evaporated to yield ethyl 10,1l-epithio-3,7,1lmediate death, the compounds of Formula A are effective trimethyldodeca-2,4-dienoate which can be purified by by reason of physiological changes caused in the treated thin layer chromatography or distillation under vacuum. insect which result in eventual death of the insect and/or The above process is repeated using each of the uninability of the treated insect to reproduce by reason of saturated esters under Column I to prepare the respective sterility or abnormal development. compound under Column H.

EXAMPLE 5 Each of N,N-dimethyl 10,11-oxido 3,7,11 trimethyltrideca 2,4 dienamide, N-methyl l0,11-oxido-3,7,11- trimethyltrideca 2,4 dienamide, N,N-isopropyl 10,11- oxido 3,7,11 trimethyltrideca 2,4 dienamide, and N,N-di-n-butyl 10,11 oxido 3,7,11 trimethyldodeca- 2,4-dienamide is used as the starting material in the process of Example 1 to prepare the respective compound, that is N,N dimethyl 10,11 epithio 3,7,11 trimethyltrideca 2,4 dienamide, N-methyl 10,11-epithio-3,7,11- trimethyltrideca 2,4 dienamide, N,N-isopropyl 10,11- epithio 3,7,1 trimethyltrideca 2,4 dienamide, and N,N-di-n-butyl 10,11 epi-thio 3,7,11 trimethyldodeca- 2,4-dienamide.

EXAMPLE 6 To a mixture of 2 g. of trans ethyl 3,7,11-trimethyldodeca 2,4,10 trienoate in 150 ml. of methylene chloride at is slowly added 1.0 molar equivalent of mchloroperbenzoic acid in 100 ml. of methylene chloride. The resulting mixture is allowed to stand for 30 minutes at 0 and then washed with 2% aqueous sodium bisulfite solution, with 5% aqueous sodium bicarbonate solution and with water, dried over sodium sulfate and evaporated to yield trans ethyl 10,11 oxido 3,7,11 trimethyldodeca-2,4-dienoate, which is purified by chromatography.

What is claimed is:

1. A compound selected from those of the following Formula A:

6 wherein R is hydrogen or alkyl of 1 to 22 carbon atoms; each of R R and R is alkyl of 1 to 12 carbon atoms; m is zero or the positive integer one, two or three; n is the positive integer one, two or three; each of R" and R is hydrogen alkyl of 1 to 12 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, aralkyl of 7 to 12 carbon atoms, phenyl, alkenyl of 2 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, alkoxyalkyl, wherein each alkyl is of 1 to 12 carbon atoms or, when taken together with the nitrogen atom to which they are attached, pyrrolidino, morpholino, piperidino, piperazino or 4-alkyl-piperazino, wherein the alkyl is of 1 to 12 carbon atoms.

2. A compound according to claim 1 wherein each of R" and R is hydrogen, methyl or ethyl; R is hydrogen or methyl; each of R and R is methyl or ethyl and R is lower alkyl.

3. A compound according to claim 2 where m is one; It is one two and'R is methyl or ethyl.

4. A compound according to claim 3 wherein R is hydrogen and n is two.

5. A compound according to claim 3 wherein R is methyl and n is two.

6. A compound according to claim 4 wherein each of R R and R is methyl.

7. A compound according to claim 5 wherein each of R R and R is methyl.

References Cited UNITED STATES PATENTS 2,729,634 1/1956 Dearborn 260-239.5 2,845,438 7/1958 Dearborn 260--327 HENRY R. JILES, Primary Examiner C. M. S. J AISLE, Assistant Examiner U.S. C1. X.R. 260-240 H p UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent NO. 3 775 ,432 Dated Nov. 27, 1973 Invencofls) John ;B. Siddall and C1ive.A. Henrick It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 1, that portion of the formula reading Signed and sealed this 16th day of July 1974.

(SEAL) Attest:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO-1050 (10-69) USCOMM-DC 6O376-P69 use GOVERNMENT PRINTING OFFICE: I969 0-366-334 

